CN105073788B - The method of the weak low concentration inverse emulsion polymerization for neutralizing polymer and the reversed-phase emulsion obtained - Google Patents
The method of the weak low concentration inverse emulsion polymerization for neutralizing polymer and the reversed-phase emulsion obtained Download PDFInfo
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- CN105073788B CN105073788B CN201480009814.XA CN201480009814A CN105073788B CN 105073788 B CN105073788 B CN 105073788B CN 201480009814 A CN201480009814 A CN 201480009814A CN 105073788 B CN105073788 B CN 105073788B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/32—Polymerisation in water-in-oil emulsions
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/04—Acids, Metal salts or ammonium salts thereof
- C08F20/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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Abstract
The present invention relates to the method for preparing polymer by polymerizeing the aqueous solution of one or more monomers in water-in-oil inverse emulsion, the one or more of monomer wherein used include at least one acid functional group, single phase with least one weak acid functional group is at least 30% for the molar percentage of all monomers used, wherein：I) in aqueous the concentration of all monomers be every gram of 1.3 mMs to 3.6 mMs of aqueous solution under conditions of polymerize, ii) in the polymerization process, be present in acid functional group on the monomer with least one acid functional group most 20% are neutralization form, and the invention further relates to the polymer that can be obtained by such method.
Description
Technical field
It is poly- the present invention relates to the synthesis comprising weak acid functional group of the thickener for being typically used as water-bearing media and/or stabilizer
The technical field of compound, is more precisely related to manufacture via reversed emulsion polymerization by least one monomer with weak acid functional group
The method of the polymer of acquisition, further relates to the polymer that can be obtained by such method.
Background of invention
The various types of polymer formed by least one monomer containing weak acid functional group are in different types of application
In be used as thickener and/or stabilizer.For example it can be mentioned that patent FR 2 810 545 and FR 2 873 126 or patent US 3
724 547.Most generally, for thickening and/or stablizing effect needed for obtaining, such polymer is with its acid functional group by least portion
The polymer form neutralized is divided directly to prepare, degree of neutralization is most often greater than 50%, or degree of neutralization even 100%.In fact, by existing
There is technology it is known that the synthetic thickening agent obtained by inverse emulsion polymerization and by the monomer containing acid functional group, such as propylene
Acid polymer, must be neutralized using preceding completely or with sufficient degree of neutralization, to obtain gratifying thickening effect.It is true
On, acid functional group, which is converted into salt, can change the state of polymer, and develop the viscosity of water-bearing media.Patent EP 0 161 038
Describe these properties.
When prepared by polymer directly carried out via water-in-oil inverse emulsion polymerization, for feasibility reason, such as in text
Offer as being illustrated in US 5 216 070, in required polymer by least one monomer comprising weak acid functional group such as third
Olefin(e) acid prepare in the case of, in order to carry out the polymerisation, it is necessary to using its weak acid functional group be in neutralization form monomer with
Avoid using via the sedimentation problem during the preparation method of reversed-phase emulsion.Such as patent US 5 380 465, US 4 539
368 and US 4 656 222 and Chinese Chemical Letters, volume 13, the 10th phase, the 993-996 pages, 2002
In open source literature using with weak acid functional group monomer high percent neutralization or even completely neutralize it is anti-phase to carry out
Emulsion polymerization.Because, it is such as in the prior art, used not neutralizing particularly shown in patent US 5 216 070
The monomer with weak acid functional group in the case of directly via reversed emulsion polymerization prepare such polymer cause precipitation/
Destabilization problems.In fact, especially preparing polyacrylic latex (such as via such method as shown in document US 3 284 393
As being specifically described in embodiment 3) cause stability problem, the latex of acquisition must be flocculated with hydrochloric acid and concentrate so as to
The polymer is obtained by filtering.
The polymer obtained by inverse emulsion polymerization is widely used as rheology modifier.Thus, still in the field is found
Show to improve the polymer of property in terms of viscosity and thickening and/or stabilizing power.For example, patent application WO 2005/
097834 provides the polymer for including acid functional group for preparing the inverse emulsions with improved thickening property.The polymerization
Thing has 25% to 100%, preferably 30% to 40% percent neutralization.
Summary of the invention
In this respect, the first purpose of applicant is the thickening for showing to improve that exploitation is obtained by inverse emulsion polymerization
The polymer of performance level.The new method of this purpose can be realized the invention provides a kind of.
In the present invention, applicant has been conceived to the anti-phase breast that polymer is prepared via water-in-oil inverse emulsion polymerization
Liquid, the reversed-phase emulsion of the polymer carries one or more weak acid comprising high molar percentage (relative to all monomers used)
The monomer of functional group, particularly includes at least 30 moles % monomer with least one weak acid functional group.The present inventor is
It is verified, using the molar percentage the monomer with weak acid functional group when, the characteristic actually one of the polymer obtained
Aspect depends on the degree of neutralization of the acid functional group of monomer used in polymerization process, on the other hand depending in aqueous phase monomer it is total dense
Degree.In the way of being created with the recommendation proposed in the prior art compared with the method that the high degree of neutralization of acid functional group is polymerize,
Applicant has turned in polyalcohol inphase opposition emulsions polymerization in the present invention, and this method shows as low degree of neutralization, particularly
The degree of neutralization of the acid functional group of most 20% presence.
In the present invention, applicant provide by water-in-oil inverse emulsion the polymerized monomer aqueous solution it is such to prepare
The method of polymer, wherein being carried out under conditions of the concentration of all monomers is every gram of 1.3 mMs to 3.6 mMs of aqueous solution
Polymerization.In addition, applicant have verified that, the higher concentration different from being used in particular for prior art, this concentration range is with being obtained
The low degree of neutralization with existing weak acid functional group polymer-compatible and can exempt in the prior art observe it is steady
Qualitative question.
In this respect, the present invention relates to by polymerize in water-in-oil inverse emulsion the aqueous solution of one or more monomers come
The method for preparing polymer, wherein the one or more of monomer used include at least one acid functional group, it is weak with least one
The single phase of acid functional group is at least 30% for the molar percentage of all monomers used, wherein：
I) in aqueous the concentration of all monomers be every gram of 1.3 mMs to 3.6 mMs of aqueous solution under conditions of enter
Row polymerization,
Ii) in the polymerization process, it is present in acid functional group on the monomer used with least one acid functional group
Most 20% be neutralization form.
Especially, in the polymerization process, it is present in the sour function on the monomer used with least one acid functional group
Most 10%, preferably up to 5% and more preferably up to the 2% of group is neutralization form, thus, it is possible to obtain even more favourable increasing
Consistence matter.According to a particular, be present in the acid functional group on monomer used 100% is in the polymerization process
Free acid form.
In the present invention, the polymerization is preferably using total monomer present in the aqueous solution as every gram of 1.7 mMs of aqueous solution
Carried out to 3.3 mMs of conditions.In the present invention, the gross weight relative to the aqueous solution (also referred to as aqueous phase) provides the monomer
Concentration, that is, the weight of the monomer included.
Especially, it is therefore possible to carry out the polymerization with following combination：
The concentration of all monomers is every gram of 1.3 mMs to 3.6 mMs of aqueous solution in the-aqueous solution, and is present in tool
Have acid functional group on the monomer of at least one acid functional group most 20%, advantageously up to 10%, preferably up to 5% and more
Preferably up to 2% or even 0% is neutralization form,
The concentration of all monomers is every gram of 1.7 mMs to 3.3 mMs of aqueous solution in the-aqueous solution, and is present in tool
Have acid functional group on the monomer of at least one acid functional group most 20%, advantageously up to 10%, preferably up to 5% and more
Preferably up to 2% or even 0% is neutralization form.
Single phase with least one weak acid functional group is preferably at least for the molar percentage of all monomers used
50%th, preferably at least 70% and very preferably at least 80%.Such molar percentage can with foregoing any monomer concentration/in
It is used together with degree combination.
In the present invention, it is preferred to carry out the polymerization with the monomer with least one olefinic degree of unsaturation.
Preferably, the polymerization is carried out with the single monomer with least one weak acid functional group, it is relative to all institutes
Be at least 30% with the molar percentage of monomer, its free acid form be selected from acrylic acid, methacrylic acid, itaconic acid, crotonic acid,
Maleic acid and fumaric acid.The monomer with least one weak acid functional group is very preferably free acid form or with according to this
The acrylic acid of the degree of neutralization of invention.It is also possible to using a variety of monomers with least one weak acid functional group, being especially selected from
Those of aforementioned list, it is at least 30% relative to the total moles percentage of all monomers used.Preferably, these monomers it
One is free acid form or the acrylic acid with the degree of neutralization according to the present invention.
The polymerization can be carried out with least one monomer with least one strong acid functional group.It is excellent in this case
Select to be less than 50% and more preferably less than 30% monomer with least one strong acid functional group relative to all monomers used
Concentration carries out the polymerization.For example the polymerization can be carried out with the monomer with least one strong acid functional group, its free acid
Form is selected from acrylamide alkyl sulfonic acid, such as 2- acrylamide-2-methylpro panesulfonic acids (ATBS).In this case, example
Such as the polymerization can be carried out with acrylic acid/ATBS or acrylic acid/ATBS/ acrylamides combination, the acid monomers may be free acid
Form, or with the degree of neutralization according to the present invention.
Subject of the present invention also can be by the polymer that the method for the present invention is obtained, and variant is implemented regardless of it.
In the present invention, it has been noted that, the model in every gram of 1.3 mMs to 3.6 mMs of aqueous solution is fallen by selection
Enclose interior monomer concentration to carry out the inverse emulsion polymerization reaction, it is possible to which preparing has low degree of neutralization or even unneutralized
The reversed-phase emulsion of polymer with acid functional group, it is stable, that is, rapid precipitation phenomenon is not observed.In addition,
Confirm such concentration range (opposite with the higher concentration particularly for prior art) and the weak neutralization knot of the acid functional group existed
The polymer for providing thickening and/or stabilized efficacy can be obtained after the step of at least part is neutralized by closing, and the effect, which is more than, to be passed through
The prior art polymer that inverse emulsion polymerization is obtained.
Term " monomer for carrying at least one acid functional group " means (to pass through with one or more free or neutralization
The effect salinization of alkali) acid functional group monomer.When monomer comprises more than an acid functional group, it is possible to only have a part
The acid functional group of neutralization form.The acid functional group of presence can be weak acid or strong acid functional group.Generally, monomer used is only included
Weak acid functional group only includes strong acid functional group, and most generally, will use the monomer with single acid functional group.
It is used as the example of the monomer with least one weak acid functional group of the free acid form of-COOH types, Ke Yiti
And acrylic acid, methacrylic acid, itaconic acid and crotonic acid, it is only comprising a weak acid functional group, and maleic acid and Fu Ma
Acid, it is thus comprising two weak acid functional groups.
As the example of the monomer with strong acid functional group of free acid form, it can be mentioned that with phosphonic acids or sulfonic acid function
The monomer of group, such as such as acrylamide alkyl sulfonic acid, 2- acrylamide-2-methylpro panesulfonic acids.
In their neutralization form, the acid functional group is anionic form, with depending on the alkali for the neutralization
Counter ion counterionsl gegenions or cation, for example, be Na when sodium hydroxide is used+Type, or when using ammoniacal liquor when be NH4 +Type.In the past,
Control the acid functional group quantity of neutralization form by selecting the pH of monomer solution, the pH can be according to the sour function of presence
The pKa of group is adjusted.
The polymerization can be related to the monomer of single type, and it is selected from the monomer with least one weak acid functional group, or relates to
And various of monomer type, it is at least one with least one weak acid functional group, is present on monomer used and is therefore present in
The ratio of the acid functional group of neutralization form on the copolymer obtained is less than or equal to 20%.Especially, except described above
The monomer with least one weak acid functional group outside, the polymer of acquisition can contain other monomers, such as carry at least one
Monomer, neutrality (or nonionic) monomer, cationic monomer and/or the monomer with hydrophobic property of strong acid functional group.No matter which
The condition of the situation of kind, aqueous phase formation and polymerization causes the acid functional group for the monomer being related to mainly to remain free acid form, and
It will not be neutralized, or be neutralized with the limited degree of neutralization less than or equal to 20% by weak by forming salinization form.When being less than
Or during neutralization equal to 20%, it is generally carried out by adding the alkali of appropriate amount in aqueous phase.Such as sodium hydroxide can be used
Or the alkali of ammoniacal liquor.
Especially, the polymerisation can be carried out with least one neutral monomer, the neutral monomer is selected from acryloyl
Amine, Methacrylamide, N, N- DMAAs, N- vinyl methylacetamides, N- vinyl formamides, vinyl acetate
Ester, DAAM, NIPA, N- [2- hydroxyls -1,1- double (hydroxymethyl) ethyls] acrylamide,
(2- hydroxyethyls) acrylate, (2,3- dihydroxypropyls) acrylate, methyl methacrylate, (2- hydroxyethyls) methyl
Acrylate, (2,3- dihydroxypropyl) methacrylate, vinyl pyrrolidone or other acrylate, or other alkene
Belong to beta-unsaturated esters.For example, 30 to 99 moles of % at least one monomer and 1 with one or more weak acid functional groups can be used
The polymerization is carried out to 70 moles of % at least one neutral monomer.The polymerization can be combined for example with acrylic acid/acrylamide
To carry out, the acrylic acid is for neutral form or with the degree of neutralization according to the present invention.
It is also possible to carrying out combined polymerization with least one cationic monomer.As the example of cationic monomer, it can be mentioned that
Diallyldialkylammonihalide salt, such as diallyldimethylammonium chloride (DADMAC)；Dialkyl aminoalkyl acrylates and
Methacrylate, particularly dialkylaminoethyl acrylates (ADAME) and methacrylic acid dialkylamino ethyl
(MADAME) acidifying or quaternized salt；Dialkylaminoalkyl acrylamide or Methacrylamide, such as metering system
Amidopropyl trimethyl ammonium chloride (MAPTAC), the acidifying of acrylamidopropyl trimethyl ammonium chloride (APTAC) or quaternary ammonium
The salt of change, and Mannich product, such as quaternized dialkylaminomethyl group acrylamide.
Acidifying salt is obtained via method known to those skilled in the art, especially by protonation.Quaternary ammonium salt dissolving is also passed through
Obtained by methods known in the art, especially by with benzyl chloride, methyl chloride (MeCl), aryl chloride, alkyl chloride or sulfuric acid two
The reaction of methyl esters.
It is also possible to carrying out combined polymerization with least one monomer with hydrophobic property.It is used as the monomer with hydrophobic property
Example, it can be mentioned that hendecanoic acid acrylamide, dodecylic acid Methacrylamide and acrylic acid derivative such as alkyl acrylate
Base ester or alkyl methacrylate, such as ethoxylation (25) methacrylic acid Shan Yu esters.
First variant of the method according to the invention, for carrying out all with least one acid functional group of the polymerization
Monomer is the monomer with least one weak acid functional group.
Second variant of the method according to the invention, except at least one monomer with least one weak acid functional group it
Outside, the polymerization is carried out with least one monomer with least one strong acid functional group.In this case, with least one
The single phase of strong acid functional group is preferably smaller than 50%, highly preferably less than 30% for the molar percentage of all monomers used.
The copolymer that the method according to the invention is obtained especially can carry at least one weak acid functional group by least one
Monomer and at least one monomer with least one strong acid functional group combination constitute, particularly by acrylic acid/ATBS groups
Close and constitute, these acid monomers are for neutral form or with the degree of neutralization according to the present invention；At least one can be carried by least one
The monomer of individual weak acid functional group carries at least one strong acid functional group with least one neutral monomer and optionally at least one
The combination of monomer is constituted, and is particularly combined by acrylic acid/acrylamide or acrylic acid/ATBS/ acrylamides combination is constituted, this third
Olefin(e) acid and the ATBS are for neutral form or with the degree of neutralization according to the present invention；At least one weak acid can be carried by least one
The monomer of functional group carries the monomer of at least one strong acid functional group with least one cationic monomer and optionally at least one
Combination constitute；Or by least one monomer with least one weak acid functional group and at least one neutral monomer and at least
A kind of combination of the monomer of cationic monomer and optionally at least one with least one strong acid functional group is constituted.
The monomer is inserted in the aqueous solution.The aqueous solution corresponds to the aqueous phase of the reversed-phase emulsion.According to the present invention, for
In the aqueous solution of the polymerization, it is present in most 20% of the acid functional group on the monomer with least one acid functional group to neutralize
Form.
Process of this invention is particularly practical for prepare water-soluble or water-swellable polymer.
Term " water-soluble polymer " means a kind of polymer, when its water with 50 g/l of concentration at 25 DEG C of temperature
In the solution without insoluble particles is obtained when being stirred.
Term " water-swellable polymer " means a kind of polymer, expands and thickens when it is in the water at 25 DEG C of temperature
The solution.
The polymer obtained in the present invention can be straight chain, structuring or crosslinking.Term " structured polymer
Thing " means the branch polymer of star or comb shape.These branch polymers are typically the non-linear polymer with side chain.Term
" cross-linked polymer " generally means that the non-linear polymer of three-dimensional network form, and its is water insoluble but is water-swellable.
When the polymer of acquisition is side chain or crosslinking, it is particularly with including two or more olefinic degrees of unsaturation
Monomer come it is branched or crosslinking.In order to constitute side chain or cross-linked polymer, at least one monomer for serving as branching agent is incorporated into
In the aqueous phase.Such reagent is selected from methylene-bisacrylamide (MBA), ethylene glycol diacrylate, dimethacrylate
Macrogol ester, diacrylamine, acrylic acid cyano methyl ester, vinyl epoxide ethyl ester, ethyleneoxy methacrylate,
Triallylamine, formaldehyde, glyoxal, glycidol ether such as ethylene glycol diglycidylether and epoxides, and its mixture.
In the present invention, it should provide, total monomer includes serving as the monomer of branching agent.
The method of the present invention is favourable for any structure for preparing straight chain, structuring or the polymer of crosslinking, and
It is particularly suitable for preparing side chain or cross-linked polymer.
It is also possible to using transfer agent, also referred to as chain limitation agent (chain limiter).Control is obtained using transfer agent
Polymer molecular weight it is particularly advantageous.As the example of transfer agent, it can be mentioned that methanol, isopropanol, sodium hypophosphite, 2- sulfydryls
Ethanol and Sodium methallyl sulfonate, and its mixture.Those skilled in the art will adjust branching agent in a known way and appoint
The amount of the transfer agent of choosing, this can wish the wish for obtaining branched polymer or cross-linked polymer according to those skilled in the art
To use.
In more detail, method of the invention comprises the following steps：
A) aqueous solution of selected monomer, referred to as aqueous phase are provided,
B) the emulsification aqueous solution in water-immiscible phase (being referred to as oil phase),
C) polymerisation is carried out.
Certainly, the step a) aqueous solution has according to total monomer of the invention, with least one weak acid functional group
Single phase for all monomers used molar percentage and the acid that is present on the monomer with least one acid functional group
The degree of neutralization of functional group.
In order to obtain required thickening effect, neutralization procedure is most commonly carried out after polymerisation, also referred to as rear neutralization procedure, so as to
At least a portion for the free acid functional group being present on the polymer is neutralized, or it is even whole.Wherein after polymerization
In the case of the step of at least part for carrying out free acid functional group present in obtained polymer is neutralized, preferably obtain
The percent neutralization of 30% to the 100% whole acid functional groups being present on the polymer.
Hereafter neutralization procedure can be carried out in many ways：
- this can be carried out to the reversed-phase emulsion that obtains at the end of the method for the present invention rear neutralize.This is typically to work as manufacturer
Itself neutralizes the situation during polymer of inverse emulsions.
- the rear neutralization can be carried out to inverting the aqueous solution obtained after the reversed-phase emulsion in water.This is typically when final
User uses the situation when reversed-phase emulsion or thus obtained powder, the deposit in the aqueous solution of referred to as stock solution
Solution be subsequently added to wait to thicken or medium to be stablized in.The end user then can freely adjust the solution
The property of polymer concentration, degree of neutralization and nertralizer.
- the rear neutralization can also be carried out to the composition containing the reversed-phase emulsion or thus obtained powder.Such combination
Thing includes other compositions according to intended application.This be typically when end user directly wait to thicken or composition to be stablized in
Use the situation when reversed-phase emulsion or thus obtained powder.With with above-mentioned situation identical mode, user can be free
Ground adjusts the property of degree of neutralization and nertralizer.
The neutralization is carried out by alkali in the way of similar to foregoing neutralization monomer, those skilled in the art can select it
Amount and property.
Generally, the polymerisation is carried out in the presence of water-in-oil emulsifier.The latter most commonly introduces the aqueous solution at it
In the oil phase of middle emulsification.Term " emulsifying agent of Water-In-Oil (W/O) type " means that its HLB value is sufficiently low, especially less than 10
HLB value is to provide the emulsifying agent of water-in-oil emulsion.
The HLB value is calculated according to relationship below：
HLB=(the weight % of hydrophilic segment)/5
The percentage by weight of hydrophilic segment is ratio of the molecular weight to the total molecular weight of the molecule of hydrophilic segment.
As the example of such water-in-oil emulsifier, it can be mentioned that surfactant polymer, such as molecular weight be 1000 to
3000 polyester, the condensation product between poly- (isobutenyl) butanedioic acid or its acid anhydrides and polyethylene glycol, molecular weight be 2500 to
3500 block copolymer, such as with titleThose sold, such as Sorbitan alcohol extracting thing, dehydration
Sorbitol monooleate, sorbitan isostearate or sorbitan sesquioleate, some polyethoxies
Change sorbitan esters, such as five ethoxylated sorbitan monoleates or five ethoxylated sorbitans are different
Stearate, or diethoxy carburetion acyl group hexadecanol or tetraethoxy lauryl acrylate.
The aqueous solution contains monomer and optional branching agent and transfer agent.It is also possible to containing complexing agent such as ethylenediamine or second
Ethylenediamine tetraacetic acid (EDTA).
Most commonly, step c) polymerization is triggered by introducing radical initiator in the emulsion of formation into step b)
Reaction.As the example of radical initiator, it can be mentioned that oxidation-reduction pair, oxidant in particular cumene hydroperoxide or uncle
Butylhydroxy peroxide, reducing agent in particular persulfate such as sodium pyrosulfite and Mohr's salt.Azo compounds can also be used
Thing such as 2,2 '-azo double (isobutyronitriles) and double (2- amidine propanes) hydrochlorides of 2,2 '-azo.
Conventionally, the usual isothermal of the polymerization, thermal insulation or carry out at controlled.That is, temperature keeps constant, lead to
Often it is 10 to 50 DEG C (isothermal), or temperature is raised (thermal insulation) naturally, the reaction is generally less than 10 DEG C in this case
At a temperature of start, final temperature is usually above 50 DEG C, or finally, and control heating is with isothermal curve and adiabatic curve
Between temperature curve.
In the method for the invention, it is possible to one or more oil-water emulsifiers are introduced at the end of polymerisation, it is excellent
At a temperature of being selected in less than 50 DEG C.
Term " emulsifying agent of oil-in-water (O/W) type " means that its HLB value is sufficiently high, particularly greater than 10 HLB value with
The emulsifying agent of oil-in-water emulsion is provided.As the example of such oil-water emulsifiers, it can be mentioned that ethoxylated sorbitan
Alcohol ester gathers such as the sorbitan oleate with the oxirane ethoxylations (EO20) of 20 equivalents, with 20 moles of ethylene oxide
The sorbitan laurate of ethoxylation, the castor oil with 40 moles of ethylene oxide polyethoxylateds, ten ethoxylations
Oleoyl decyl alcohol, seven ethoxylated lauryls or the anhydrosorbitol monostearate with 20 moles of ethylene oxide polyethoxylateds
Ester.
In the present invention, the amount of the emulsifying agent of introducing causes the reversed-phase emulsion of the polymer obtained to usually contain 1 weight %
Water-In-Oil (W/O) types of emulsifiers to 10 weight %, preferably 2.5 weight % to 9 weight %, and optional 2 weight % to 10
Weight %, preferably 2.5 weight % to 6 weight % oil-in-water (O/W) types of emulsifiers.
Generally, aqueous phase is 50/50 to 90/10 to the weight ratio of oil phase.
The oil phase can be for example made up of mineral oil, particularly commercial mineral oil, containing close under environment temperature (22 DEG C)
Spend paraffinic hydrocarbonses, saturation isoparaffin, saturation cycloalkane or the naphthalene type saturated hydrocarbons for 0.7 to 0.9；It is made up of vegetable oil；By
Artificial oil such as Nexbase 2004 or Parleam composition；It is made up of ester such as octyl stearate or butyl oleate；By vegetable oil
Saualane such as plant origin is constituted；Or be made up of several mixtures of these oil.
At the end of the polymerisation, it is possible to which the emulsion of acquisition is diluted or concentrated.Li particular, it is possible to pass through distillation
Concentrate the emulsion obtained or be completely dried to obtain powder.Such concentration or drying can be previously-introduced or no advance
Carried out in the case of the emulsifying agent for introducing oil-in-water (O/W) type.
Subject of the present invention also have be by the present invention method obtain water-in-oil inverse emulsion form polymer, nothing
How implement variant by it.
The polymer that the method according to the invention is obtained before they are used as thickener and/or stabilizer in usually requiring
And step.In the case of not additional neutralization procedure, the present invention polymer in, the acid functional group existed it is most
20%, preferably up to 10%, even more preferably at most 5%, most preferably up to 2% is neutralization form.The acid functional group of presence
This low degree of neutralization provides high flexibility in use to user, enables a user to by then adjusting degree of neutralization
Section is to degree needed for him, so that the property of regulation polymer and effect needed for thus adjusting when in use, particularly thicken and/or
Stablizing effect.Such method also allows the property of user's selection nertralizer used, compatible with intended applications.The invention further relates to
Then impose neutralization procedure using obtain neutralize acid functional group relative to all acid functional groups present on polymer percentage as
30% to 100% such polymer.
Thus these polymer neutralized provide much better thickening property, and remaining all conditions is not with complying with the present invention's
The polymer phase obtained by inverse emulsion polymerization of concentration and neutrality condition defined in method compares all same.Particularly in
Afterwards, gathered from being made up of same monomer in high degree of neutralization and/or under different total monomers by reversed-phase emulsion
The polymer phase ratio directly prepared is closed, the polymer provides favourable property.
Advantageously, the polymer obtained by the method for the present invention is in the complete free acid functional group for neutralizing presence or at least
Can more effectively it be thickened and/or stabilized aqueous medium after neutralizing to a greater extent.
The reversed-phase emulsion obtained using the method for the present invention can be concentrated for example by distilling.Then obtain its polymer
Concentration can be 30 weight % to 75 weight %, preferably 40 weight % to 65 weight % reversed-phase emulsion.
Separating step then is imposed so that in powder type, it is also to the polymer of the reversed-phase emulsion obtained from the present invention
The part of the present invention.Such separating step for example can be selected from precipitation, azeotropic distillation and spray drying technology.
In fact, in the present invention, it is possible to concentrate or separate leave the present invention method when directly obtain it is anti-phase
The polymer of emulsion form, the favorable property without losing the polymer obtained.Especially there are a variety of anti-phase breasts by polymer
The method that liquid obtains powder, it includes separating active material with other compositions of emulsion, for example：
- precipitated from non-solvent medium, the non-solvent medium such as acetone, methanol or polymer do not dissolve in therein
What its polar solvent.Simple filtering is then able to separation of polymeric composition granule；
- the azeotropic distillation in the presence of agglomerant (agglomerating agent) and stabilization of polymers can make
Make before particle drying is carried out easily by the aggregation being separated by filtration；
- spray drying is included in the cloud for the fine droplets for manufacturing emulsion in controlled period in stream of hot air.
Embodiment
I. the embodiment of acrylic acid/sodium acrylate base homopolymer is prepared
Embodiment 1：
The composition of aqueous phase is added in 1 liter of beaker under magnetic stirring：
- 150 grams of ice-cold acrylic acid
- 605 grams of deionized waters
- 0.023 gram of sodium hypophosphite
- 0.10 gram of diethylene triamine pentacetic acid (DTPA) sodium
- 0.075 gram of methylene-bisacrylamide
- 0.15 gram of sodium bromate
Then, in 1 liter of glass reactor, organic phase is prepared with following component under magnetic stirring：
- 102 grams of aliphatic hydrocarbons (Isopar L)
- 98 grams of White Mineral Oils (Marcol 152)
- 20 grams of sorbitol monooleates
- 25 grams of polymerization stabilizers (Hypermer 1083)
The aqueous phase is progressively transferred in the organic phase.The pre-emulsion being consequently formed then imposes Strong shear 1 minute
(Ultra Turrax, IKA).
The reversed-phase emulsion is then deaerated 30 minutes by simple nitrogen bubble.
The aqueous solution of sodium pyrosulfite containing 1.0 weight % then with 2.5 mls/hour of flow velocity through 1 hour 30 points
Clock is added.Once reaching maximum temperature, the temperature of reactant mixture is kept for 60 minutes, then cooling.
Finally, the tridecanol of 40 grams of ethoxylations (6 moles) is added at about 30 DEG C.
Embodiment 2：
The composition of aqueous phase is added in 1 liter of beaker under magnetic stirring：
- 175 grams of ice-cold acrylic acid
- 580 grams of deionized waters
- 0.03 gram of sodium hypophosphite
- 0.10 gram of diethylene triamine pentacetic acid (DTPA) sodium
- 0.087 gram of methylene-bisacrylamide
- 0.15 gram of sodium bromate
Then, the preparation of organic phase and the remainder of the preparation method are carried out according to embodiment 1.
Embodiment 3：
The composition of aqueous phase is added in 1 liter of beaker under magnetic stirring：
- 100 grams of ice-cold acrylic acid
- 655 grams of deionized waters
- 0.02 gram of sodium hypophosphite
- 0.10 gram of diethylene triamine pentacetic acid (DTPA) sodium
- 0.05 gram of methylene-bisacrylamide
- 0.15 gram of sodium bromate
Then, the preparation of organic phase and the remainder of the preparation method are carried out according to embodiment 1.
Embodiment 4：Neutralize 3.5%/concentration 2.76
Process same as Example 1 is carried out, 5.83 gram of 50% sodium hydroxide solution is added in aqueous phase, passed through simultaneously
The amount for adjusting deionized water keeps the identical weight of aqueous phase.
Embodiment 5：Neutralize 19%/concentration 3.5
The composition of aqueous phase is added in 1 liter of beaker under magnetic stirring：
- 190 grams of ice-cold acrylic acid
- 40 gram of 50% sodium hydroxide solution
- 525 grams of deionized waters
- 0.03 gram of sodium hypophosphite
- 0.10 gram of diethylene triamine pentacetic acid (DTPA) sodium
- 0.095 gram of methylene-bisacrylamide
- 0.15 gram of sodium bromate
Then, the preparation of organic phase and the remainder of the preparation method are carried out according to embodiment 1.
Comparative example 1：
The composition of aqueous phase is added in 1 liter of beaker under magnetic stirring：
- 50 grams of ice-cold acrylic acid
- 705 grams of deionized waters
- 0.01 gram of sodium hypophosphite
- 0.10 gram of diethylene triamine pentacetic acid (DTPA) sodium
- 0.043 gram of methylene-bisacrylamide
- 0.15 gram of sodium bromate
Then, the preparation of organic phase and the remainder of the preparation method are carried out according to embodiment 1.
Comparative example 2：
The composition of aqueous phase is added in 1 liter of beaker under magnetic stirring：
- 199 grams of ice-cold acrylic acid
- 115 gram of 50% sodium hydroxide solution
- 441 grams of deionized waters
- 0.03 gram of sodium hypophosphite
- 0.10 gram of diethylene triamine pentacetic acid (DTPA) sodium
- 0.15 gram of methylene-bisacrylamide
- 0.15 gram of sodium bromate
Then, the preparation of organic phase and the remainder of the preparation method are carried out according to embodiment 1.
Comparative example 3：
The composition of aqueous phase is added in 1 liter of beaker under magnetic stirring：
- 199 grams of ice-cold acrylic acid
- 556 grams of deionized waters
- 0.03 gram of sodium hypophosphite
- 0.10 gram of diethylene triamine pentacetic acid (DTPA) sodium
- 0.1 gram of methylene-bisacrylamide
- 0.15 gram of sodium bromate
Then, the preparation of organic phase is carried out according to embodiment 1.
The aqueous phase is progressively transferred in the organic phase.The pre-emulsion being consequently formed then imposes Strong shear 1 minute
(Ultra Turrax, IKA).
The reversed-phase emulsion is then deaerated 30 minutes by simple nitrogen bubble.
The aqueous solution of sodium pyrosulfite containing 1.0 weight % is then added with 2.5 mls/hour of flow velocity.In reduction
Property solution is initially added into rear moment, and the emulsion unstability simultaneously then condenses.It can not be polymerize, the system is unstable.
Comparative example 4:
The composition of aqueous phase is added in 1 liter of beaker under magnetic stirring：
- 150 grams of ice-cold acrylic acid
- 83 gram of 50% sodium hydroxide solution
- 522 grams of deionized waters
- 0.023 gram of sodium hypophosphite
- 0.10 gram of diethylene triamine pentacetic acid (DTPA) sodium
- 0.75 gram of methylene-bisacrylamide
- 0.15 gram of sodium bromate
Then, the preparation of organic phase and the remainder of the preparation method are carried out according to embodiment 1.
Polymer characterization
Step：[0.16 weight %] measures the viscosity of aqueous solutions of polymers under isoconcentration
250 grams of deionized waters are placed in 400 milliliters of beakers, then, (three blades, 500 revs/min under mechanical stirring
Clock), the desired amount of reversed-phase emulsion is gradually added into obtain the solution of the living polymer containing 0.16 weight %.Then use hydrogen-oxygen
Change sodium to adjust pH to 7+/- 0.1.Under the pH, be present in the acid functional group on the polymer 100% is neutralized.Make this molten
Liquid continues to stir 15 minutes, then stands 5 minutes.Then Brookfield is used with module 4 and 20 revs/min of rotary speed
RVT viscosity meter viscosity.
As a result record in table 1.
Table 1
ET75 is the reversed-phase emulsion of commercially available acrylate homopolymer, and the 50% of its acid functional group neutralizes before polymerization.
The polymer obtained by the reversed emulsion polymerization of the present invention has than the condition by not complying with the present invention
The much better thickening effect of polymer that antiphase emulsifiable method is obtained.
It is highly effective at very low concentrations according to the polymer that the present invention is obtained.
II. relative to the comparative studies of the antiphase emulsifiable method and polymer proposed in the prior art
The thickening effect of the polymer obtained more as described in the prior art by inverse emulsion polymerization and according to this hair
The thickening effect of the polymer of bright acquisition, all other condition all same.
The embodiment of various prior art literatures is repeated, only changes concentration and/or percent neutralization to meet the present invention.Connect
, viscosity is measured using the reversed-phase emulsion and according to scheme same as above.
Hereinafter, AA represents acrylic acid, and AM represents acrylamide, and ATBS represents 2- acrylamido -2- methyl-prop sulphurs
Acid.
a.EP 0 161 038
Embodiment 1A and 1B that repetition is described on the 5-6 pages of patent EP 0 161 038.Embodiment 1A and 1B with
After be modified to meet the present invention.
Embodiment 6
Embodiment 6 corresponds to embodiment 1A, wherein reducing the amount of acrylamide, acrylic acid and MBA monomers and instead going
Ionized water, to obtain same amount of aqueous phase, and the total monomer of aqueous phase is 2.8 mMs/gram, rather than 4.9.
Embodiment 7
Embodiment 7 corresponds to embodiment 1A, wherein the regulation of type in the same manner as in Example 6 is carried out, to obtain 3.5 mmoles
You/gram aqueous phase total monomer, rather than 4.9.
Embodiment 8
Embodiment 8 corresponds to embodiment 1B, wherein the regulation in terms of carrying out the monomer of type same as above, and be additionally added
Ammoniacal liquor is to neutralize 20% acid functional group, to obtain the total monomer of 2.8 mMs/gram, rather than 4.9.
Embodiment 9
Embodiment 9 corresponds to embodiment 1B, wherein the regulation of type in the same manner as in Example 8 is carried out, to obtain aqueous phase
The total monomer of 3.5 mMs/gram, rather than 4.9.
As a result record in table 2.
Table 2
These embodiments confirm the advantage of the weak neutralization with reference to low monomer concentration and the monomer comprising acid functional group.It is such
Selection can significantly improve the thickening property of acquisition.
b.EP 0 503 853
The embodiment 1,2 and 7 described on repeat patent EP 0 503 853 the 5-6 pages.The embodiment 1,2 and 7 are subsequent
It is modified to meet the present invention.
Embodiment 10
Embodiment 10 corresponds to embodiment 1, wherein reduction acrylic monomers and NaOH amount and instead deionized water, with
Identical aqueous phase amount is obtained, the total monomer of aqueous phase is 3.4 mMs/gram, rather than in 4.3, and acid functional group and percentage
Than for 15%, rather than 100%.
Embodiment 11
Embodiment 11 corresponds to embodiment 2, wherein reducing acrylic monomers, NaOH and MBA amount and instead deionization
Water, to obtain identical aqueous phase amount, the total monomer of aqueous phase is 3.4 mMs/gram, rather than 4.3, and acid functional group is neutralized
Percentage is 15%, rather than 100%.
Embodiment 12
Embodiment 12 corresponds to embodiment 2, wherein reduction acrylamide and acrylic monomers and MBA and NaOH amount are simultaneously
Instead deionized water, with the sour function of the total monomer for the aqueous phase for obtaining 3.4 mMs/gram, rather than 4.3, and 15%
Group's percent neutralization, rather than 100%.
As a result record in table 3.
Table 3
These experiments also show the advantage of the method for the present invention compared with the method for the prior art.Even viscosity wherein
In the case of the relatively low straight chain polymer of holding (embodiment 1 from EP 0 503 853, and embodiment 10), when using this
During the method for invention, the viscosity of acquisition is double, and this meets significantly improving for performance level.
The combination of two kinds of essential characteristics of the present invention, the i.e. low concentration of monomer and the low neutralization of the monomer comprising acid functional group
Degree is combined, and the polymer for providing improved thickening effect can be obtained in the case of presence or absence of branching agent.
c.WO 2005/097834
The embodiment 2 that repetition is described on patent WO 2005/097834 page 14.Then reduction percent neutralization and
Monomer concentration is to meet of the invention (embodiment 13).
As a result record in table 4.
Table 4
Again, these experiments show advantage of the method for the present invention compared with art methods, because it can
Significantly improve the thickening capabilities of the polymer of acquisition.
d.US 4 677 152
Repeat the embodiment 2 on the columns of patent US 4 677 152 the 8th.Percent neutralization and monomer concentration is reduced immediately to meet
(embodiment 14) of the invention.
As a result record in table 5.
Table 5
Again, the combination of two kinds of essential characteristics of the invention, i.e., the low concentration of monomer is with including acid functional group in aqueous phase
Monomer low degree of neutralization combine, result in the polymer that bigger thickening effect is provided.
e.EP 0 645 429
Repeat the embodiment 3 on patent application EP 0 645 429 page 5.Percent neutralization is then reduced to meet this
Invent (embodiment 15 and 16).
As a result record in table 6.
Table 6
When the condition using the present invention, the polymer of acquisition has the thickening effect greatly improved.
Claims (35)
1. by polymerizeing the method that the aqueous solution of one or more monomers prepares polymer, wherein institute in water-in-oil inverse emulsion
At least one acid functional group is included with the one or more of monomer, the single phase with least one weak acid functional group is for all
The molar percentage of monomer used is at least 30%, wherein：
I) in aqueous the concentration of all monomers be every gram of 1.3 mMs to 3.6 mMs of aqueous solution under conditions of gathered
Close,
Ii) in the polymerization process, it is present in most 20% of the acid functional group on the monomer with least one acid functional group
To neutralize form.
2. the method for claim 1, wherein it is present in the polymerization process with least one acid functional group
Most 10% of acid functional group on monomer are neutralization form.
3. method as claimed in claim 1 or 2, wherein all acid functional groups being present on the monomer are in the polymerization process
In be free acid form.
4. the concentration of method as claimed in claim 1 or 2, the wherein polymerization all monomers in aqueous is every gram of aqueous solution
Carried out under conditions of 1.7 mMs to 3.3 mMs.
5. method as claimed in claim 1 or 2, wherein the single phase with one or more weak acid functional groups is for acid
The molar percentage of all monomers used of functional group is at least 50%.
6. method as claimed in claim 1 or 2, wherein all monomers used are the lists with least one olefinic degree of unsaturation
Body.
7. the choosing of the monomer with least one weak acid functional group of method as claimed in claim 1 or 2, wherein free acid form
From acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid and fumaric acid.
8. method as claimed in claim 1 or 2, wherein carrying out the polymerization, the neutral monomer with least one neutral monomer
Selected from acrylamide, Methacrylamide, N, N- DMAAs, N- vinyl methylacetamides, N- vinyl formyls
Amine, vinyl acetate, DAAM, NIPA, N- [double (hydroxymethyl) ethyls of 2- hydroxyls -1,1-]
Acrylamide, (2- hydroxyethyls) acrylate, (2,3- dihydroxypropyls) acrylate, methyl methacrylate, (2- hydroxyls
Ethyl) methacrylate, (2,3- dihydroxypropyls) methacrylate and vinyl pyrrolidone.
9. the method as described in claim 1, wherein all monomers used with least one acid functional group are to carry one
Or the monomer of multiple weak acid functional groups.
10. method as claimed in claim 9, wherein polymerize with the mixture of acrylic acid/acrylamide monomer, and it is described
Acid functional group is according to the degree of neutralization shown in claim 1,2 or 3.
11. the method as described in claim 1, wherein being carried out with least one monomer with one or more strong acid functional groups
The polymerization.
12. method as claimed in claim 11, wherein with the monomer with one or more strong acid functional groups less than 50%
Molar percentage relative to all monomers used carries out the polymerization.
13. the method as described in claim 11 or 12, wherein free acid form with one or more strong acid functional groups
Monomer is selected from acrylamide alkyl sulfonic acid.
14. the method as described in claim 10 or 11, wherein with 2- acrylamide-2-methylpro panesulfonic acids/acrylic monomers
Mixture or the mixture of 2- acrylamide-2-methylpro panesulfonic acids/acrylic acid/acrylamide monomer carry out the polymerization, and
Acid functional group is according to the degree of neutralization shown in claim 1,2 or 3.
15. method as claimed in claim 1 or 2, the wherein aqueous phase contain at least one monomer for serving as branching agent so that should
Polymerization obtains the polymer of crosslinking.
16. method as claimed in claim 15, the wherein branching agent are selected from methylene-bisacrylamide (MBA), diacrylate
Glycol ester, PEGDMA-400, diacrylamine, acrylic acid cyano methyl ester, vinyl epoxide ethyl ester,
Ethyleneoxy methacrylate, triallylamine, formaldehyde, glyoxal, glycidol ether and epoxides, and its mixing
Thing.
17. method as claimed in claim 1 or 2, the wherein polymerisation are carried out in the presence of water-in-oil emulsifier.
18. method as claimed in claim 1 or 2, wherein carrying out neutralizing at least one be present on polymer after polymerisation
The step of free acid functional group in part.
19. method as claimed in claim 1 or 2, it uses transfer agent, and the transfer agent is selected from methanol, isopropanol, hypophosphorous acid
Sodium, 2 mercapto ethanol and Sodium methallyl sulfonate, and its mixture.
20. the method as described in claim 1, it comprises the following steps：
A) aqueous solution of selected monomer, referred to as aqueous phase are provided,
B) aqueous solution is emulsified in the water-immiscible phase of referred to as oil phase,
C) polymerisation is carried out.
21. method as claimed in claim 20, the wherein aqueous phase are 50/50 to 90/10 to the weight ratio of oil phase.
22. the method as described in claim 20 or 21, the wherein oil phase are by being 0.7 to 0.9 containing density at ambient temperature
Paraffinic hydrocarbonses, saturation isoparaffin, the mineral oil composition of saturation cycloalkane or naphthalene type saturated hydrocarbons；It is made up of vegetable oil；By
Artificial oil is constituted；It is made up of one or more esters；Or be made up of several mixtures of these oil.
23. the method as described in claim 20 or 21, wherein the oil phase contains water-in-oil emulsifier, in the oil phase reclaimed water
Solution is emulsified.
24. the method as described in claim 20 or 21, wherein being drawn by introducing free radical in the emulsion of formation into step b)
Agent is sent out to trigger step c) polymerisation.
25. the method as described in claim 1 or 20, wherein, after the polymerization, introduce one or more oil-water emulsifiers.
26. the method as described in claim 1 or 20, wherein, after the polymerisation, the emulsion of acquisition is diluted or concentrated.
27. the method as described in claim 1 or 20, wherein carrying out being present in the polymer of acquisition after the polymerisation
The step of at least part of free acid functional group is neutralized.
28. the neutralization acid functional group that method as claimed in claim 27, the wherein neutralization procedure are obtained is relative on polymer
The percentage of all acid functional groups existed is 30% to 100%.
29. a kind of reversed-phase emulsion, it contains the polymer obtained by the method according to claim 1 or 20.
30. reversed-phase emulsion as claimed in claim 29, wherein in the polymer, most the 20% of the acid functional group existed
To neutralize form.
31. reversed-phase emulsion as claimed in claim 30, wherein the polymer after then carrying out neutralization procedure in obtaining
With acid functional group relative to all acid functional groups present on polymer percentage be 30% to 100%.
32. the reversed-phase emulsion as described in claim 29 or 30, wherein the polymer is side chain or crosslinking.
33. the reversed-phase emulsion as described in claim 29 or 30, wherein the polymer is powder after separating step is then carried out
Last form.
34. reversed-phase emulsion as claimed in claim 33, wherein the separating step is selected from precipitation, azeotropic distillation and spray drying
Technology.
35. the reversed-phase emulsion as described in claim 29 or 30, wherein the polymer is water-soluble or water-swellable.
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| FR1351498 | 2013-02-21 | ||
| FR1351498A FR3002229B1 (en) | 2013-02-21 | 2013-02-21 | PROCESS FOR LOW CONCENTRATION REVERSE EMULSION POLYMERIZATION OF LOWLY NEUTRALIZED POLYMERS AND INVERSE EMULSIONS OBTAINED |
| PCT/FR2014/050338 WO2014128400A1 (en) | 2013-02-21 | 2014-02-18 | Process for low-concentration, inverse emulsion polymerization of weakly neutralized polymers and inverse emulsions obtained |
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| WO2014159233A1 (en) | 2013-03-14 | 2014-10-02 | Ecolab Usa Inc. | Methods for increasing retention and drainage in papermaking processes |
| FR3011464B1 (en) * | 2013-10-07 | 2015-11-20 | Snf Sas | COSMETIC USE OF POLYMERS OBTAINED BY LOW CONCENTRATION REVERSE EMULSION POLYMERIZATION WITH A LOW RATE OF NEUTRALIZED MONOMERS |
| US10442980B2 (en) * | 2014-07-29 | 2019-10-15 | Ecolab Usa Inc. | Polymer emulsions for use in crude oil recovery |
| FR3024736B1 (en) | 2014-08-06 | 2016-08-26 | Snf Sas | USE IN DETERGENT COMPOSITIONS OF POLYMERS OBTAINED BY LOW-CONCENTRATION REVERSE EMULSION POLYMERIZATION WITH A LOW RATE OF NEUTRALIZED MONOMERS |
| AR107710A1 (en) | 2016-02-23 | 2018-05-23 | Ecolab Usa Inc | HYDRAZIDE INTERRUPTED POLYMER EMULSIONS FOR USE IN RECOVERY OF CRUDE OIL |
| FR3075219B1 (en) | 2017-12-14 | 2019-11-22 | S.P.C.M. Sa | COMPOSITION COMPRISING A WATER-SOLUBLE POLYMER (CO) ENCAPSULATED IN AN ENVELOPE AND USE IN THE ASSISTED RECOVERY OF PETROLEUM AND GAS |
| CN109627380B (en) * | 2018-12-11 | 2021-09-07 | 广州天赐高新材料股份有限公司 | Cation inverse emulsion thickener and preparation method thereof |
| FR3122092B1 (en) * | 2021-04-22 | 2024-02-23 | Snf Sa | USE IN A HYDROALCOHOLIC COMPOSITION OF POLYMERS OBTAINED BY LOW CONCENTRATION REVERSE EMULSION POLYMERIZATION WITH A LOW RATE OF NEUTRALIZED MONOMERS |
| CN113583176B (en) * | 2021-08-20 | 2022-12-27 | 西南石油大学 | Switch emulsion drag reducer and preparation method and application thereof |
| CN115449017B (en) * | 2022-10-09 | 2023-08-15 | 山东诺尔生物科技有限公司 | Star polymer filtrate reducer and preparation method thereof |
| CN115594795A (en) * | 2022-11-11 | 2023-01-13 | 中国石油天然气集团有限公司（Cn） | Salt-resistant and temperature-resistant fracturing fluid thickening agent, preparation method thereof and fracturing fluid |
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| FR3002229B1 (en) | 2015-03-13 |
| US9290588B2 (en) | 2016-03-22 |
| BR112015017605B1 (en) | 2021-01-19 |
| US9963532B2 (en) | 2018-05-08 |
| US20140309368A1 (en) | 2014-10-16 |
| BR112015017605A2 (en) | 2017-07-11 |
| MX2015010467A (en) | 2016-02-22 |
| CN105073788A (en) | 2015-11-18 |
| FR3002229A1 (en) | 2014-08-22 |
| MX359239B (en) | 2018-09-20 |
| EP2958948B1 (en) | 2016-11-30 |
| ES2615350T3 (en) | 2017-06-06 |
| WO2014128400A1 (en) | 2014-08-28 |
| EP2958948A1 (en) | 2015-12-30 |
| US20160152749A1 (en) | 2016-06-02 |
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